CA2252538A1 - Fungicide mixtures - Google Patents
Fungicide mixtures Download PDFInfo
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- CA2252538A1 CA2252538A1 CA002252538A CA2252538A CA2252538A1 CA 2252538 A1 CA2252538 A1 CA 2252538A1 CA 002252538 A CA002252538 A CA 002252538A CA 2252538 A CA2252538 A CA 2252538A CA 2252538 A1 CA2252538 A1 CA 2252538A1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
This invention concerns fungicide mixtures containing in a synergistically effective amount a1) a carbamate of the formula (I), in which T stands for CH or N, n is 0, 1 or 2, and R stands for halogen, C1-C4-alkyl, C1-C4-alkyl halide, where the radicals R can be different if n is 2, and/or a2) an oxime ether of the formula (II), in which the substituents have the following meaning: X is oxygen or amino (NH), Y is CH or N; Z is oxygen, sulphur, amino (NH) or C1-C4-alkyl amino (N-C1-C4-alkyl); R' is C1-C6-alkyl, C1-C6-alkyl halide, C3-C6-alkenyl, C2-C6-alkenyl halide, C3-C6-alkinyl, C3-C6-alkinyl halide, C3-C6-cycloalkyl-methyl or benzyl, which can be either partially or completely halogenated and/or can carry one to three of the following radicals; cyano, C1-C4-alkyl, C1-C4-alkyl halide, C1-C4-alkoxy, C1-C4-alkoxy halide, and C1-C4-alkylthio, and b) an organic tin compound of the formula (III), in which L- stands for a hydroxy or acetate group.
Description
'; 0050/46788 CA 022~2~38 1998-10-21 .
~ungicide mixtures The present invention relates to a fungicidal mixture which 5 comprises al) a carbamate of the formula I
~ ~ o ~ T
~OCH3 ~ Rn O
where T is CH or N, n is 0, 1 or 2 and R is halogen, Cl-C4-alkyl or Cl-C4-haloalkyl, it being possible for the radicals R to be different when n is 2, and/or a2) an oxime ether of the formula II
1~1 , 0 ~ NOCH3 CH3X~ YOCH3 Z-R' where the substituents have the following meaning:
X is oxygen or amino (NH);
Y is CH or N;
Z is oxygen, sulfur, amino (NH) or Cl-C4-alkylamino (N-Cl-C4-alkyl);
R' is Cl-C6-alkyl, Cl-C6-haloalkyl, C3-C6-alkenyl, C2-4-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl-methyl, or benzyl which may be partially or fully halogenated and/or may carry one to three of the following radicals: cyano, Cl-C4-alkyl, C1-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and Cl-C4-alkylthio;
and b) an organotin compound of the formula III
~ ~ 0050/46788 CA 022~2~38 1998-10-21 ¢~1 (Ill) where L- is a hydroxyl or acetate group, in a synergistically active amount.
Moreover, the invention relates to me~hods of controlling harmful fungi with mixtures of the compounds I and/or II and III and to the use of the compounds I and II and III for the preparation of such mixtures.
The compounds of the formula I, their preparation and their action against harmful fungi have been disclosed in the literature (WO-A 96/01,256 and WO-A 96/01,258).
20 Compounds of the formula II, their preparation and their action against harmful fungi have been described in WO-A 95/21,153, WO-A 95/21 154 and DE-A 19 528 651Ø
The compounds III (L- = OH-: CAS RN: [76-87-9]; common name:
25 fentin hydroxide; L- = CH3CO2-: US-A 3,499,086; common name:
fentin acetate), their preparation and their action against harmful fungi have also been disclosed.
It was an object of the present inventions [sic] to provide 30 mixtures which have an improved activity gainst harmful fungi combined with a reduced total amount of active ingredients applied (synergistic mixtures) with a view to reducing the rates of application and to improving the spectrum of action of the known compounds.
Accordingly, we have found that this object is achieved by the mixture defined at the outset. Moreover, we have found that better control of the harmful fungi is possible by applying the compounds I and/or II and the compound III simultaneously 40 together or separately or by applying the compound I and/or II
and the compounds III in succession than when the individual compounds are used.
The invention covers binary mixtures of compounds I or II and III
45 and also ternary mixtures of I, II and III.
.
0050/46788 CA 022~2~38 1998-10-21 In particular, the formula I represents carbamates in which-the combination of the substituents corresponds to one line of the table which follows:
5 Table 1:
No. T Rn I.l N 2-F
I.2 N 3-F
I.3 N 4-F
I.4 N 2-Cl I.5 N 3-Cl I.6 N 4-Cl I.7 N 2-Br I.8 N 3-Br I.9 N 4-Br I.10 N 2-CH3 I.11 N 3-CH3 I.12 N 4-CH3 I.13 N 2-CH2CH3 I.14 N 3-CH2CH3 I.15 N 4-CH2CH3 I.16 N 2-CH(CH3)2 I.17 N 3-CH(CH3)2 I.18 N 4-CH(CH3)2 I.19 N 2-CF3 I.20 N 3-CF3 I.21 N 4-CF3 I.22 N 2,4-F2 I.23 N 2,4-C12 I.24 N 3,4-C12 I.25 N 2-Cl, 4-CH3 I.26 N 3-Cl, 4-CH3 I.27 CH 2-F
I.28 CH 3-F
I.29 CH 4-F
I.30 CH 2-Cl I.31 CH 3-Cl I.32 CH 4-Cl I.33 CH 2-Br I.34 CH 3-Br , 0050/46788 CA 022~2~38 1998-10-21 No. T Rn I.35 CH 4-Br I.36 CH 2-CH3 I.37 CH 3-CH3 I.38 CH 4-CH3 I.39 CH 2-CH2CH3 I.40 CH 3-CH2CH3 I.41 - CH 4-CH2CH3 I.42 CH 2-CH(CH3)2 I.43 CH 3-CH(CH3)2 I.44 CH 4-CH(CH3)2 I.45 CH 2-CF3 I.46 CH 3-CF3 I.47 CH 4-CF3 I.48 CH 2,4-F2 I.49 CH 2,4-C12 I.50 CH 3,4-C12 I.51 CH 2-Cl, 4-CH3 I.52 CH 3-Cl, 4-CH3 25 The compounds I.12, I.23, I.32 and I.38 are especially preferred.
The general formula II represents in particular oxime ethers where X is oxygen and Y is CH or where X is amino and Y is N.
30 Furthermore, preference is given to compounds II where Z is oxy-gen.
Likewise, preference is given to compounds II where R' is alkyl or benzyl.
With a view to their use in the synergistic mixtures according to the invention, compounds II which are particularly preferred are those listed in the tables below:
., 0050/46788 CA 022~2~38 1998-10-21 Table 2.
Compounds of the formula IIA where for each compound ZR~ cor-responds to one row in Table A
CH]N ~ CH] (IA) Table 3.
Compounds of the formula ~B [sic], where for each compound ZR~
15 corresponds to one row in Table A
~~ 0 ~;~ NOCH3 (IB) CH30 CHOCH3 Z-R' Table A:
25 No. ZR~
II.l o-cH2cH2cH3 II.2 0-CH(CH3)2 II.3 0-CH2CH2CH2CH3 30II.4 0-CH(CH3)CH2CH3 II.5 0-CH2CH(CH3)2 II.6 o-C(CH3)3 II.7 S-C(CH3)3 II.8 0-CH(CH3)CH2CH2CH3 II.9 0-CH2C(CH3)3 II.10 0-C(Cl)=CC12 II.ll 0-CH2CH=CH-Cl ( trans) II.12 O-cH2-c(cH3)=cH2 40 II.13 O-CH2-(cyclopropyl) II.14 o-CH2-C6H5 II.15 o-cH2-[4-F-c6H4]
II.16 0-CH2CH3 45II.17 0-CH(CH2CH3)2 .
0050/46788 CA 022~2~38 1998-10-21 In relation to the C=Y double bond, the compounds of the formula II can be present in the E or the Z configuration (in relation to the carboxylic acid function). Accordingly, they can be used in the mixture according to the invention in each case either in the 5 form of pure E or Z isomers or else in the form of an E/Z isomer mixture. The E/Z isomer mixture or the E isomer is preferably used, the E isomer of the compounds II being especially pre-ferred.
10 The C=N double bonds of the oxime ether groups in the side chain of the compounds II can exist in each case in the form of pure E
or Z isomers or in the form of E/Z isomer mixtures. The compounds II can be used in the mixtures according to the invention as iso-mer mixtures or else as the pure isomers. With a view to their 15 use, compounds II which are particularly preferred are those where the terminal oxime ether group in the side chain is in the cis configuration (OCH3 group to ZR').
Due to their basic character, the compounds I and II are capable 20 of forming adducts or salts with inorganic or organic acids or with metal ions.
Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and 25 hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic 30 acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, ci nn~mi C acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having from 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic acids (aromatic radicals such as phenyl and naphthyl 35 which have attached to them one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of from 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as phenyl and naphthyl which have attached to them one or 40 two phosphoric [sic] acid radicals), it being possible for the alkyl or aryl radicals to have attached to them further substituents, eg. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.
.
0050/46788 CA 022~2~38 1998-10-21 Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, and of the third and fourth main group, in particular aluminum, tin and lead, and of the first to eighth sub-group, in particular 5 chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Especially preferred are the metal ions of the elements of the sub-groups of the fourth period. The metals can in this case be in the various valences which they can assume.
10 When preparing the mixtures, it is preferred to employ the pure active ingredients I, II and III, with which further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be A~m; Yed, if so desired.
The mixtures of the compounds I and/or II and III, or the simultaneous joint or separate use of the compounds I and/or II
and III, are distinguished by an outstAn~;ng activity against a broad spectrum of phytopathogenic fungi, in particular from the 20 classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically and can therefore be employed as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of 25 fungi in a variety of crop plants such as cotton, vegetable species (eg. cucumbers, beans and curcubits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soybeans, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe gr~m;n;s (powdery mildew)~on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on curcubits, Podosphaera leucotricha on apples, Puccinia species on 35 cereals, Rhizoctonia species on cotton, rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinera [sic] (gray mold) on strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola 40 on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora cubense on cucurbits, Plasmopara viticola on grapevines, Pseudoperonospora species on cucurbits and hops, Alternaria species on vegetables and fruit, 45 and Fusarium and Verticillium species.
- ~ 0050/46788 CA 022~2~38 1998-10-21 .
Furthermore, they can be used in the protection of materials (eg.
in the protection of wood), for example against Paecilomyces variotii.
5 The compounds I, II and III can be applied simultaneously together or separately or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
.
10 The compounds I and III or II and III are normally used in a weight ratio of from 10:1 to 0.1:1, preferably 5:1 to 0.2:1, in particular S:1 to 1:1.
The application rates of the mixtures according to the invention - 15 are in general from 0.01 to 3 kg/ha, preferably 0.1 to 1.5 kg/ha, in particular 0.1 to 1.0 kg/ha, depending on the nature of the desired effect.
In the case of the compounds I and/or II, the application rates 20 are as a rule from 0.01 to 0.5 kg/ha, preferably 0.05 to 0.5 kg/ha, in particular 0.05 to 0.4 kg/ha.
.
Correspondingly, in the case of the compounds III, the application rates are normally from 0.01 to 0.5 kg/ha, preferably 25 0.05 to 0.5 kg/ha, in particular 0.05 to 0.4 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 50 g/kg seed, preferably 0.01 to 10 g/kg, in particular 0.01 to 8 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and/or II and III or of the mixtures of the compounds I and/or II and III is effected by spraying or dusting the seeds, the plants or the 35 soils before or after sowing of the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention can be formulated for example in the form of ready-to-spray 40 solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, and applied by spraying, atomizing, dusting, spreading or pouring. The use form depends on the 45 intended purpose; in any case, it should guarantee as fine and 0050/46788 CA 022~2~38 1998-10-21 uniform as possible a distribution of the mixture according-to the invention.
The formulations are prepared in a m~nner known per se, eg. by 5 adding solvents and/or carriers. It is usual to admix inert additives, such as emulsifiers or dispersants, with the formulations.
Suitable surfactants are the alkali metal salts, alkaline earth 10 metal salts and ammonium salts of aromatic sulfonic acids, eg.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol 15 ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenol [sic] ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol [sic] polyglycol ethers or 20 tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or jointly grinding the compounds I and/or II and III or the mixture of the compounds I, II and III with a solid carrier.
30 Granules (eg. coated granules, impregnated granules or homogeneous granules) are normally prepared by binding the active ingredient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths such 35 as silica gel, silicas, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, 40 and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise from 0.1 to 95% by weight, 45 preferably 0.5 to 90% by weight, of one of the compounds I and/or II and III, or of the mixture of the compounds I and/or II and III. The active ingredients are employed in a purity of from 90%
..
OOSO/46788 CA 022~2~38 1998-10-21 ~ 10 to 100%, preferably 95% to 100% (according to NMR or HPLC
spectrum [sic]).
The compounds I and/or II and III, or the mixtures, or the 5 corresponding formulations, are applied by treating the harmful fungi or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally active amount of the mixture, or of the compounds I and/or II and III in the case of separate application. Application can be effected before or after 10 infection by the harmful fungi.
The fungicidal activity of the compounds and of the mixtures is demonstrated by the following experiments:
15 The active ingredients, separately or together, are formulated as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil~ LN (Lutensol~ AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor~ EL (Emulan~ EL, 20 emulsifier based on ethoxylated fatty alcohols) and diluted with water to give the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The 25 expected efficacies of the mixtures of the active ingredients are determined using Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Colby's formula:
E = x + y - x y/100 E expected efficacy, expressed in % of the untreated control, when using the mixture of the active ingredients A and B at concentrations of a and b x efficacy, expressed in % of the untreated control, when using active ingredient A at a concentratlon of a 40 y efficacy, expressed in % of the untreated control, when using active ingredient B at a concentration of b The efficacy (W) is calculated as follows using Abbot's formula:
W = (1 ~ 100/~
OOSO/46788 CA 022~2~38 1998-10-21 ~ is the fungal infection of the treated plants in % and -~ is the fungal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants are not infected.
10 Examples 1 - 12 Activity against Phytophthora infestans in tomatoes Leaves of potted plants of the variety UGroBe Fleischtomate" were 15 sprayed with an aqueous suspension prepared from a stock solution of 10% of active compound, 63% of cyclohexanone and 27% of emul-sifier until dripping wet. The following day, the leaves were infected with an aqueous zoospore suspension of Phytophthora infestans. The plants were then placed in a chamber saturated 20 with water vapor at 16-18~C. After 6 days, the tomato blight on the infected untreated control plants had developed to such an extent that the infestation could be assessed visually in %.
The visually determined percentages of infected leaf area were 25 converted into efficacies in % of the untreated control. An effi-cacy of 0 indicates the same degree of infestation as in the un-treated control, an efficacy of 100 is 0% infestation. The effi-cacies to be expected for active compound combinations were de-termined by the Colby formula (Colby, S.R. Calculating synergi-30 stic and antagonistic responses of herbicide combinations",Weeds, 15, p. 20-22, 1967) and compared to the observed effica-cies.
Table 4 Ex. Active compound Concentration Efficacy in % of of active com- the untreated pound in the control spray liquor in ppm 40 lv Control (untreated) (99 % infe- 0 station) 2v Compound No. I.32 = A 0.06 40 0.015 40 3v Compound No. I.38 = B 0.06 60 0.015 10 . 0050/46788 CA 022~2~38 l998-l0-2l Ex.Active compound Concentration Efficacy in % of ~ of active com- the untreated pound in the control spray liquor in ppm 4vIIa = Fentin-hydroxide 0.06 75 . 0.015 50 5vIIb = Fentin-acetate 0.06 0 0.015 0 Table 5 Ex.Concentration of Observed efficacy Calculated active compound in efficacy*) the spray liquor ~ 15 in ppm 6 0.06 A 97 85 0.06 IIIa 7 0.015 A 85 70 20 0.015 IIIa 8 0.06 A 97 39 +
0.06 IIIb 9 0.015 A 80 39 +
0.015 IIIb 10 0.06 B 100 90 +
0.06 IIIa 30 110.06 B 93 60 0.06 IIIb 12 0.015 B 30 9 +
0.015 IIIb * Calculated by the Colby formula Examples 13 - 25 Activity against Phytophthora infestans in tomatoes Leaves of potted plants of the variety "Gro~e Fleischtomate~ were sprayed with an aqueous suspension prepared from a stock solution of 10% of active compound, 63% of cyclohexanone and 27% of emul-sifier until dripping wet. The following day, the leaves were 45 infected with an aqueous zoospore suspension of Phytophthora infestans. The plants were then placed in a chamber saturated with water vapor at 16-18 C. After 6 days, the tomato blight on . . . .
0050/46788 CA 022~2~38 1998-10-21 the infected untreated control plants had developed to such-an extent that the infestation could be assessed visually in %.
The visually determined percentages of infected leaf area were 5 converted into efficacies in % of the untreated control. An effi-cacy of 0 indicates the same degree of infestation as in the un-treated control, an efficacy of 100 is 0% infestation. The effi-cacies to be expected for active compound combinations were de-ter~ined by the Colby formula (Colby, S.R. ~'Calculating synergi-lO stic and antagonistic responses of herbicide combinations",Weeds, 15, p. 20-22, 1967) and compared to the observed effica-cies.
Table 6 Ex. Active compound Concentration Efficacy in %
of active com- of the untrea-pound in the ted control spray liquor in . ppm 20 13v Control (untreated)(99 % infest- 0 ation) 14v C = Tab. 2A, No. 2 0.06 0 0.015 0 15v D = Tab. 2A, No. 4 0.06 0 0.015 o 16v IIa = Fentin-hydroxide0.06 75 0.015 50 17v IIb = Fentin-acetate 0.06 0 0.015 0 Table 7 Ex.Concentration of Observed efficacy Calculated active compound in efficacy*) the spray liquor in ppm 18 0.06 C 100 75 +
0.06 IIIa 19 0.015 C 100 50 0.015 IIIa 0.06 C 100 0 0.06 IIIb 21 0.015 C 97 0 +
0.015 IIIb Ex. Concentration of Observed efficacy Calculated active compound in efficacy*) the spray liquor in ppm 5 22 0.06 D 100 75 0.06 IIIa 23 0.015 D 100 50 +
0.015 IIIa 24 0.06 D . 100 0 0.06 IIIb 0.015 D 100 0 +
0.015 IIIb
~ungicide mixtures The present invention relates to a fungicidal mixture which 5 comprises al) a carbamate of the formula I
~ ~ o ~ T
~OCH3 ~ Rn O
where T is CH or N, n is 0, 1 or 2 and R is halogen, Cl-C4-alkyl or Cl-C4-haloalkyl, it being possible for the radicals R to be different when n is 2, and/or a2) an oxime ether of the formula II
1~1 , 0 ~ NOCH3 CH3X~ YOCH3 Z-R' where the substituents have the following meaning:
X is oxygen or amino (NH);
Y is CH or N;
Z is oxygen, sulfur, amino (NH) or Cl-C4-alkylamino (N-Cl-C4-alkyl);
R' is Cl-C6-alkyl, Cl-C6-haloalkyl, C3-C6-alkenyl, C2-4-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl-methyl, or benzyl which may be partially or fully halogenated and/or may carry one to three of the following radicals: cyano, Cl-C4-alkyl, C1-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy and Cl-C4-alkylthio;
and b) an organotin compound of the formula III
~ ~ 0050/46788 CA 022~2~38 1998-10-21 ¢~1 (Ill) where L- is a hydroxyl or acetate group, in a synergistically active amount.
Moreover, the invention relates to me~hods of controlling harmful fungi with mixtures of the compounds I and/or II and III and to the use of the compounds I and II and III for the preparation of such mixtures.
The compounds of the formula I, their preparation and their action against harmful fungi have been disclosed in the literature (WO-A 96/01,256 and WO-A 96/01,258).
20 Compounds of the formula II, their preparation and their action against harmful fungi have been described in WO-A 95/21,153, WO-A 95/21 154 and DE-A 19 528 651Ø
The compounds III (L- = OH-: CAS RN: [76-87-9]; common name:
25 fentin hydroxide; L- = CH3CO2-: US-A 3,499,086; common name:
fentin acetate), their preparation and their action against harmful fungi have also been disclosed.
It was an object of the present inventions [sic] to provide 30 mixtures which have an improved activity gainst harmful fungi combined with a reduced total amount of active ingredients applied (synergistic mixtures) with a view to reducing the rates of application and to improving the spectrum of action of the known compounds.
Accordingly, we have found that this object is achieved by the mixture defined at the outset. Moreover, we have found that better control of the harmful fungi is possible by applying the compounds I and/or II and the compound III simultaneously 40 together or separately or by applying the compound I and/or II
and the compounds III in succession than when the individual compounds are used.
The invention covers binary mixtures of compounds I or II and III
45 and also ternary mixtures of I, II and III.
.
0050/46788 CA 022~2~38 1998-10-21 In particular, the formula I represents carbamates in which-the combination of the substituents corresponds to one line of the table which follows:
5 Table 1:
No. T Rn I.l N 2-F
I.2 N 3-F
I.3 N 4-F
I.4 N 2-Cl I.5 N 3-Cl I.6 N 4-Cl I.7 N 2-Br I.8 N 3-Br I.9 N 4-Br I.10 N 2-CH3 I.11 N 3-CH3 I.12 N 4-CH3 I.13 N 2-CH2CH3 I.14 N 3-CH2CH3 I.15 N 4-CH2CH3 I.16 N 2-CH(CH3)2 I.17 N 3-CH(CH3)2 I.18 N 4-CH(CH3)2 I.19 N 2-CF3 I.20 N 3-CF3 I.21 N 4-CF3 I.22 N 2,4-F2 I.23 N 2,4-C12 I.24 N 3,4-C12 I.25 N 2-Cl, 4-CH3 I.26 N 3-Cl, 4-CH3 I.27 CH 2-F
I.28 CH 3-F
I.29 CH 4-F
I.30 CH 2-Cl I.31 CH 3-Cl I.32 CH 4-Cl I.33 CH 2-Br I.34 CH 3-Br , 0050/46788 CA 022~2~38 1998-10-21 No. T Rn I.35 CH 4-Br I.36 CH 2-CH3 I.37 CH 3-CH3 I.38 CH 4-CH3 I.39 CH 2-CH2CH3 I.40 CH 3-CH2CH3 I.41 - CH 4-CH2CH3 I.42 CH 2-CH(CH3)2 I.43 CH 3-CH(CH3)2 I.44 CH 4-CH(CH3)2 I.45 CH 2-CF3 I.46 CH 3-CF3 I.47 CH 4-CF3 I.48 CH 2,4-F2 I.49 CH 2,4-C12 I.50 CH 3,4-C12 I.51 CH 2-Cl, 4-CH3 I.52 CH 3-Cl, 4-CH3 25 The compounds I.12, I.23, I.32 and I.38 are especially preferred.
The general formula II represents in particular oxime ethers where X is oxygen and Y is CH or where X is amino and Y is N.
30 Furthermore, preference is given to compounds II where Z is oxy-gen.
Likewise, preference is given to compounds II where R' is alkyl or benzyl.
With a view to their use in the synergistic mixtures according to the invention, compounds II which are particularly preferred are those listed in the tables below:
., 0050/46788 CA 022~2~38 1998-10-21 Table 2.
Compounds of the formula IIA where for each compound ZR~ cor-responds to one row in Table A
CH]N ~ CH] (IA) Table 3.
Compounds of the formula ~B [sic], where for each compound ZR~
15 corresponds to one row in Table A
~~ 0 ~;~ NOCH3 (IB) CH30 CHOCH3 Z-R' Table A:
25 No. ZR~
II.l o-cH2cH2cH3 II.2 0-CH(CH3)2 II.3 0-CH2CH2CH2CH3 30II.4 0-CH(CH3)CH2CH3 II.5 0-CH2CH(CH3)2 II.6 o-C(CH3)3 II.7 S-C(CH3)3 II.8 0-CH(CH3)CH2CH2CH3 II.9 0-CH2C(CH3)3 II.10 0-C(Cl)=CC12 II.ll 0-CH2CH=CH-Cl ( trans) II.12 O-cH2-c(cH3)=cH2 40 II.13 O-CH2-(cyclopropyl) II.14 o-CH2-C6H5 II.15 o-cH2-[4-F-c6H4]
II.16 0-CH2CH3 45II.17 0-CH(CH2CH3)2 .
0050/46788 CA 022~2~38 1998-10-21 In relation to the C=Y double bond, the compounds of the formula II can be present in the E or the Z configuration (in relation to the carboxylic acid function). Accordingly, they can be used in the mixture according to the invention in each case either in the 5 form of pure E or Z isomers or else in the form of an E/Z isomer mixture. The E/Z isomer mixture or the E isomer is preferably used, the E isomer of the compounds II being especially pre-ferred.
10 The C=N double bonds of the oxime ether groups in the side chain of the compounds II can exist in each case in the form of pure E
or Z isomers or in the form of E/Z isomer mixtures. The compounds II can be used in the mixtures according to the invention as iso-mer mixtures or else as the pure isomers. With a view to their 15 use, compounds II which are particularly preferred are those where the terminal oxime ether group in the side chain is in the cis configuration (OCH3 group to ZR').
Due to their basic character, the compounds I and II are capable 20 of forming adducts or salts with inorganic or organic acids or with metal ions.
Examples of inorganic acids are hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and 25 hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic 30 acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, ci nn~mi C acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having from 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic acids (aromatic radicals such as phenyl and naphthyl 35 which have attached to them one or two sulfo groups), alkylphosphonic acids (phosphonic acids having straight-chain or branched alkyl radicals of from 1 to 20 carbon atoms), arylphosphonic acids or -diphosphonic acids (aromatic radicals such as phenyl and naphthyl which have attached to them one or 40 two phosphoric [sic] acid radicals), it being possible for the alkyl or aryl radicals to have attached to them further substituents, eg. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.
.
0050/46788 CA 022~2~38 1998-10-21 Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, and of the third and fourth main group, in particular aluminum, tin and lead, and of the first to eighth sub-group, in particular 5 chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Especially preferred are the metal ions of the elements of the sub-groups of the fourth period. The metals can in this case be in the various valences which they can assume.
10 When preparing the mixtures, it is preferred to employ the pure active ingredients I, II and III, with which further active ingredients against harmful fungi or other pests such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active ingredients or fertilizers can be A~m; Yed, if so desired.
The mixtures of the compounds I and/or II and III, or the simultaneous joint or separate use of the compounds I and/or II
and III, are distinguished by an outstAn~;ng activity against a broad spectrum of phytopathogenic fungi, in particular from the 20 classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them act systemically and can therefore be employed as foliar- and soil-acting fungicides.
They are especially important for controlling a large number of 25 fungi in a variety of crop plants such as cotton, vegetable species (eg. cucumbers, beans and curcubits), barley, grass, oats, coffee, maize, fruit species, rice, rye, soybeans, grapevine, wheat, ornamentals, sugar cane, and a variety of seeds.
They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe gr~m;n;s (powdery mildew)~on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on curcubits, Podosphaera leucotricha on apples, Puccinia species on 35 cereals, Rhizoctonia species on cotton, rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinera [sic] (gray mold) on strawberries, vegetables, ornamentals and grapevines, Cercospora arachidicola 40 on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Pseudoperonospora cubense on cucurbits, Plasmopara viticola on grapevines, Pseudoperonospora species on cucurbits and hops, Alternaria species on vegetables and fruit, 45 and Fusarium and Verticillium species.
- ~ 0050/46788 CA 022~2~38 1998-10-21 .
Furthermore, they can be used in the protection of materials (eg.
in the protection of wood), for example against Paecilomyces variotii.
5 The compounds I, II and III can be applied simultaneously together or separately or in succession, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
.
10 The compounds I and III or II and III are normally used in a weight ratio of from 10:1 to 0.1:1, preferably 5:1 to 0.2:1, in particular S:1 to 1:1.
The application rates of the mixtures according to the invention - 15 are in general from 0.01 to 3 kg/ha, preferably 0.1 to 1.5 kg/ha, in particular 0.1 to 1.0 kg/ha, depending on the nature of the desired effect.
In the case of the compounds I and/or II, the application rates 20 are as a rule from 0.01 to 0.5 kg/ha, preferably 0.05 to 0.5 kg/ha, in particular 0.05 to 0.4 kg/ha.
.
Correspondingly, in the case of the compounds III, the application rates are normally from 0.01 to 0.5 kg/ha, preferably 25 0.05 to 0.5 kg/ha, in particular 0.05 to 0.4 kg/ha.
For seed treatment, the application rates of the mixture are generally from 0.001 to 50 g/kg seed, preferably 0.01 to 10 g/kg, in particular 0.01 to 8 g/kg.
If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and/or II and III or of the mixtures of the compounds I and/or II and III is effected by spraying or dusting the seeds, the plants or the 35 soils before or after sowing of the plants, or before or after plant emergence.
The fungicidal synergistic mixtures according to the invention can be formulated for example in the form of ready-to-spray 40 solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, and applied by spraying, atomizing, dusting, spreading or pouring. The use form depends on the 45 intended purpose; in any case, it should guarantee as fine and 0050/46788 CA 022~2~38 1998-10-21 uniform as possible a distribution of the mixture according-to the invention.
The formulations are prepared in a m~nner known per se, eg. by 5 adding solvents and/or carriers. It is usual to admix inert additives, such as emulsifiers or dispersants, with the formulations.
Suitable surfactants are the alkali metal salts, alkaline earth 10 metal salts and ammonium salts of aromatic sulfonic acids, eg.
ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylarylsulfonates, of alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol 15 ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenol [sic] ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol [sic] polyglycol ethers or 20 tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, materials for spreading and dusts can be prepared by mixing or jointly grinding the compounds I and/or II and III or the mixture of the compounds I, II and III with a solid carrier.
30 Granules (eg. coated granules, impregnated granules or homogeneous granules) are normally prepared by binding the active ingredient, or active ingredients, to a solid carrier.
Fillers or solid carriers are, for example, mineral earths such 35 as silica gel, silicas, silica gels [sic], silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, 40 and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.
The formulations generally comprise from 0.1 to 95% by weight, 45 preferably 0.5 to 90% by weight, of one of the compounds I and/or II and III, or of the mixture of the compounds I and/or II and III. The active ingredients are employed in a purity of from 90%
..
OOSO/46788 CA 022~2~38 1998-10-21 ~ 10 to 100%, preferably 95% to 100% (according to NMR or HPLC
spectrum [sic]).
The compounds I and/or II and III, or the mixtures, or the 5 corresponding formulations, are applied by treating the harmful fungi or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a fungicidally active amount of the mixture, or of the compounds I and/or II and III in the case of separate application. Application can be effected before or after 10 infection by the harmful fungi.
The fungicidal activity of the compounds and of the mixtures is demonstrated by the following experiments:
15 The active ingredients, separately or together, are formulated as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil~ LN (Lutensol~ AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor~ EL (Emulan~ EL, 20 emulsifier based on ethoxylated fatty alcohols) and diluted with water to give the desired concentration.
Evaluation is carried out by determining the infected leaf areas in percent. These percentages are converted into efficacies. The 25 expected efficacies of the mixtures of the active ingredients are determined using Colby's formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Colby's formula:
E = x + y - x y/100 E expected efficacy, expressed in % of the untreated control, when using the mixture of the active ingredients A and B at concentrations of a and b x efficacy, expressed in % of the untreated control, when using active ingredient A at a concentratlon of a 40 y efficacy, expressed in % of the untreated control, when using active ingredient B at a concentration of b The efficacy (W) is calculated as follows using Abbot's formula:
W = (1 ~ 100/~
OOSO/46788 CA 022~2~38 1998-10-21 ~ is the fungal infection of the treated plants in % and -~ is the fungal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants are not infected.
10 Examples 1 - 12 Activity against Phytophthora infestans in tomatoes Leaves of potted plants of the variety UGroBe Fleischtomate" were 15 sprayed with an aqueous suspension prepared from a stock solution of 10% of active compound, 63% of cyclohexanone and 27% of emul-sifier until dripping wet. The following day, the leaves were infected with an aqueous zoospore suspension of Phytophthora infestans. The plants were then placed in a chamber saturated 20 with water vapor at 16-18~C. After 6 days, the tomato blight on the infected untreated control plants had developed to such an extent that the infestation could be assessed visually in %.
The visually determined percentages of infected leaf area were 25 converted into efficacies in % of the untreated control. An effi-cacy of 0 indicates the same degree of infestation as in the un-treated control, an efficacy of 100 is 0% infestation. The effi-cacies to be expected for active compound combinations were de-termined by the Colby formula (Colby, S.R. Calculating synergi-30 stic and antagonistic responses of herbicide combinations",Weeds, 15, p. 20-22, 1967) and compared to the observed effica-cies.
Table 4 Ex. Active compound Concentration Efficacy in % of of active com- the untreated pound in the control spray liquor in ppm 40 lv Control (untreated) (99 % infe- 0 station) 2v Compound No. I.32 = A 0.06 40 0.015 40 3v Compound No. I.38 = B 0.06 60 0.015 10 . 0050/46788 CA 022~2~38 l998-l0-2l Ex.Active compound Concentration Efficacy in % of ~ of active com- the untreated pound in the control spray liquor in ppm 4vIIa = Fentin-hydroxide 0.06 75 . 0.015 50 5vIIb = Fentin-acetate 0.06 0 0.015 0 Table 5 Ex.Concentration of Observed efficacy Calculated active compound in efficacy*) the spray liquor ~ 15 in ppm 6 0.06 A 97 85 0.06 IIIa 7 0.015 A 85 70 20 0.015 IIIa 8 0.06 A 97 39 +
0.06 IIIb 9 0.015 A 80 39 +
0.015 IIIb 10 0.06 B 100 90 +
0.06 IIIa 30 110.06 B 93 60 0.06 IIIb 12 0.015 B 30 9 +
0.015 IIIb * Calculated by the Colby formula Examples 13 - 25 Activity against Phytophthora infestans in tomatoes Leaves of potted plants of the variety "Gro~e Fleischtomate~ were sprayed with an aqueous suspension prepared from a stock solution of 10% of active compound, 63% of cyclohexanone and 27% of emul-sifier until dripping wet. The following day, the leaves were 45 infected with an aqueous zoospore suspension of Phytophthora infestans. The plants were then placed in a chamber saturated with water vapor at 16-18 C. After 6 days, the tomato blight on . . . .
0050/46788 CA 022~2~38 1998-10-21 the infected untreated control plants had developed to such-an extent that the infestation could be assessed visually in %.
The visually determined percentages of infected leaf area were 5 converted into efficacies in % of the untreated control. An effi-cacy of 0 indicates the same degree of infestation as in the un-treated control, an efficacy of 100 is 0% infestation. The effi-cacies to be expected for active compound combinations were de-ter~ined by the Colby formula (Colby, S.R. ~'Calculating synergi-lO stic and antagonistic responses of herbicide combinations",Weeds, 15, p. 20-22, 1967) and compared to the observed effica-cies.
Table 6 Ex. Active compound Concentration Efficacy in %
of active com- of the untrea-pound in the ted control spray liquor in . ppm 20 13v Control (untreated)(99 % infest- 0 ation) 14v C = Tab. 2A, No. 2 0.06 0 0.015 0 15v D = Tab. 2A, No. 4 0.06 0 0.015 o 16v IIa = Fentin-hydroxide0.06 75 0.015 50 17v IIb = Fentin-acetate 0.06 0 0.015 0 Table 7 Ex.Concentration of Observed efficacy Calculated active compound in efficacy*) the spray liquor in ppm 18 0.06 C 100 75 +
0.06 IIIa 19 0.015 C 100 50 0.015 IIIa 0.06 C 100 0 0.06 IIIb 21 0.015 C 97 0 +
0.015 IIIb Ex. Concentration of Observed efficacy Calculated active compound in efficacy*) the spray liquor in ppm 5 22 0.06 D 100 75 0.06 IIIa 23 0.015 D 100 50 +
0.015 IIIa 24 0.06 D . 100 0 0.06 IIIb 0.015 D 100 0 +
0.015 IIIb
Claims (8)
1. A fungicidal mixture comprising al) a carbamate of the formula I
where T is CH or N, n is 0, 1 or 2 and R is halogen, C1-C4-alkyl or C1-C4-haloalkyl, it being possible for the radicals R to be different when n is 2, and/or a2) an oxime ether of the formula II
where the substituents have the following meaning:
X is oxygen or amino (NH);
Y is CH or N;
Z is oxygen, sulfur, amino (NH) or C1-C4-alkylamino (N-C1-C4-alkyl);
R' is C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C2-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl-methyl, or benzyl which may be partially or fully halogenated and/or may carry one to three of the following radicals: cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-alkylthio;
and b) an organotin compound of the formula III
where L- is a hydroxyl or acetate group, in a synergistically active amount.
where T is CH or N, n is 0, 1 or 2 and R is halogen, C1-C4-alkyl or C1-C4-haloalkyl, it being possible for the radicals R to be different when n is 2, and/or a2) an oxime ether of the formula II
where the substituents have the following meaning:
X is oxygen or amino (NH);
Y is CH or N;
Z is oxygen, sulfur, amino (NH) or C1-C4-alkylamino (N-C1-C4-alkyl);
R' is C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C2-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkyl-methyl, or benzyl which may be partially or fully halogenated and/or may carry one to three of the following radicals: cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-alkylthio;
and b) an organotin compound of the formula III
where L- is a hydroxyl or acetate group, in a synergistically active amount.
2. A fungicidal mixture as claimed in claim 1 wherein the weight ratio of the compound I or II to the compound III is 10:1 to 0.1:1.
3. A method of controlling harmful fungi, which comprises treating the harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free from them with a compound of the formula I and/or II as set forth in claim 1 and a compound of the formula III as set forth in claim 1.
4. A method as claimed in claim 3, wherein a compound I or II
and the compound III are applied simultaneously together or separately or in succession.
and the compound III are applied simultaneously together or separately or in succession.
5. A method as claimed in claim 3, wherein the harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free from them are treated with from 0.01 to 0.5 kg/ha of a compound I and/or II.
6. A method as claimed in claim 3, wherein the harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free from them are treated with from 0.01 to 0.5 kg/ha of a compound III.
7. The use of the compounds I and/or II as set forth in claim 1 for the preparation of fungicidally active synergistic mixtures.
8. The use of the compounds III as set forth in claim 1 for the preparation of fungicidally active synergistic mixtures.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19616721.3 | 1996-04-26 | ||
| DE19616721 | 1996-04-26 | ||
| DE19616686.1 | 1996-04-26 | ||
| DE19616686 | 1996-04-26 | ||
| DE19635508 | 1996-09-02 | ||
| DE19635508.7 | 1996-09-02 | ||
| PCT/EP1997/002022 WO1997040684A1 (en) | 1996-04-26 | 1997-04-22 | Fungicide mixtures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2252538A1 true CA2252538A1 (en) | 1997-11-06 |
Family
ID=27216186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002252538A Abandoned CA2252538A1 (en) | 1996-04-26 | 1997-04-22 | Fungicide mixtures |
Country Status (25)
| Country | Link |
|---|---|
| US (1) | US6124336A (en) |
| EP (1) | EP0900018B1 (en) |
| JP (1) | JP2000509055A (en) |
| KR (1) | KR20000065008A (en) |
| CN (1) | CN1213950A (en) |
| AR (1) | AR006861A1 (en) |
| AT (1) | ATE204132T1 (en) |
| AU (1) | AU732263B2 (en) |
| BR (1) | BR9708792A (en) |
| CA (1) | CA2252538A1 (en) |
| CO (1) | CO4761031A1 (en) |
| CZ (1) | CZ289270B6 (en) |
| DE (1) | DE59704313D1 (en) |
| DK (1) | DK0900018T3 (en) |
| EA (1) | EA001170B1 (en) |
| ES (1) | ES2163151T3 (en) |
| GR (1) | GR3036533T3 (en) |
| IL (1) | IL125394A0 (en) |
| MX (1) | MX9806349A (en) |
| NZ (1) | NZ331122A (en) |
| PL (1) | PL329508A1 (en) |
| PT (1) | PT900018E (en) |
| SK (1) | SK135998A3 (en) |
| TW (1) | TW330835B (en) |
| WO (1) | WO1997040684A1 (en) |
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| AP2005003313A0 (en) * | 2002-11-15 | 2005-06-30 | Basf Ag | Fungicidal mixtures |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0035467A1 (en) * | 1980-03-04 | 1981-09-09 | Schweizerische Aluminium Ag | Process for producing foamed plastic boards |
| DE3701715A1 (en) * | 1987-01-22 | 1988-08-04 | Bayer Ag | Fungicidal drug combinations |
| ES2196054T3 (en) * | 1994-02-04 | 2003-12-16 | Basf Ag | DERIVATIVES OF PHENYLACETIC ACID, PROCEDURE AND INTERMEDIATE PRODUCTS FOR OBTAINING AND AGENTS CONTAINING THE SAME. |
| BR9506719A (en) * | 1994-02-04 | 1997-09-23 | Basf Ag | Compounds derived from phenylacetic acid Process for preparing the same composition against animal pests or harmful fungi Process to combat animal pests or harmful fungi and use of the compounds |
| DE4423612A1 (en) * | 1994-07-06 | 1996-01-11 | Basf Ag | 2 - [(Dihydro) pyrazolyl-3'-oxymethylene] anilides, process for their preparation and their use |
| DE4423613A1 (en) * | 1994-07-06 | 1996-01-11 | Basf Ag | 2- [1 ', 2', 4'-triazole-3'yloxymethylene] anilides, process for their preparation and their use |
| DE19528651A1 (en) * | 1995-08-04 | 1997-02-06 | Basf Ag | Hydroximic acid derivatives, process for their preparation and compositions containing them |
-
1997
- 1997-04-22 JP JP9538538A patent/JP2000509055A/en active Pending
- 1997-04-22 WO PCT/EP1997/002022 patent/WO1997040684A1/en not_active Application Discontinuation
- 1997-04-22 PT PT97921688T patent/PT900018E/en unknown
- 1997-04-22 CN CN97193127A patent/CN1213950A/en active Pending
- 1997-04-22 SK SK1359-98A patent/SK135998A3/en unknown
- 1997-04-22 IL IL12539497A patent/IL125394A0/en unknown
- 1997-04-22 AT AT97921688T patent/ATE204132T1/en not_active IP Right Cessation
- 1997-04-22 AU AU27669/97A patent/AU732263B2/en not_active Ceased
- 1997-04-22 KR KR1019980708545A patent/KR20000065008A/en not_active Application Discontinuation
- 1997-04-22 BR BR9708792A patent/BR9708792A/en unknown
- 1997-04-22 CZ CZ19983292A patent/CZ289270B6/en not_active IP Right Cessation
- 1997-04-22 DK DK97921688T patent/DK0900018T3/en active
- 1997-04-22 PL PL97329508A patent/PL329508A1/en unknown
- 1997-04-22 CA CA002252538A patent/CA2252538A1/en not_active Abandoned
- 1997-04-22 NZ NZ331122A patent/NZ331122A/en unknown
- 1997-04-22 EA EA199800902A patent/EA001170B1/en not_active IP Right Cessation
- 1997-04-22 US US09/171,565 patent/US6124336A/en not_active Expired - Fee Related
- 1997-04-22 DE DE59704313T patent/DE59704313D1/en not_active Expired - Lifetime
- 1997-04-22 EP EP97921688A patent/EP0900018B1/en not_active Expired - Lifetime
- 1997-04-22 ES ES97921688T patent/ES2163151T3/en not_active Expired - Lifetime
- 1997-04-25 CO CO97022202A patent/CO4761031A1/en unknown
- 1997-04-25 TW TW086105455A patent/TW330835B/en active
- 1997-04-25 AR ARP970101713A patent/AR006861A1/en unknown
-
1998
- 1998-08-06 MX MX9806349A patent/MX9806349A/en not_active Application Discontinuation
-
2001
- 2001-09-05 GR GR20010401393T patent/GR3036533T3/en not_active IP Right Cessation
Also Published As
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|---|---|
| EA199800902A1 (en) | 1999-06-24 |
| ES2163151T3 (en) | 2002-01-16 |
| DE59704313D1 (en) | 2001-09-20 |
| BR9708792A (en) | 1999-08-03 |
| EA001170B1 (en) | 2000-10-30 |
| ATE204132T1 (en) | 2001-09-15 |
| AR006861A1 (en) | 1999-09-29 |
| SK135998A3 (en) | 1999-02-11 |
| TW330835B (en) | 1998-05-01 |
| CO4761031A1 (en) | 1999-04-27 |
| AU732263B2 (en) | 2001-04-12 |
| NZ331122A (en) | 2000-06-23 |
| EP0900018B1 (en) | 2001-08-16 |
| US6124336A (en) | 2000-09-26 |
| GR3036533T3 (en) | 2001-12-31 |
| CZ329298A3 (en) | 1999-04-14 |
| WO1997040684A1 (en) | 1997-11-06 |
| PL329508A1 (en) | 1999-03-29 |
| CN1213950A (en) | 1999-04-14 |
| JP2000509055A (en) | 2000-07-18 |
| DK0900018T3 (en) | 2001-10-08 |
| AU2766997A (en) | 1997-11-19 |
| IL125394A0 (en) | 1999-03-12 |
| CZ289270B6 (en) | 2001-12-12 |
| EP0900018A1 (en) | 1999-03-10 |
| MX9806349A (en) | 1998-10-31 |
| KR20000065008A (en) | 2000-11-06 |
| PT900018E (en) | 2002-02-28 |
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